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研究生:HUYNH TAN THANH
研究生(外文):HUYNH TAN THANH
論文名稱:PdxNiy Bimetallic Nanocatalysts for Green Production of Hydrogen Peroxide
論文名稱(外文):PdxNiy Bimetallic Nanocatalysts for Green Production of Hydrogen Peroxide
指導教授:黃炳照黃炳照引用關係林昇佃
指導教授(外文):Bing-Joe HwangShawn D. Lin
口試委員:黃炳照林昇佃
口試委員(外文):Bing-Joe HwangShawn D. Lin
口試日期:2015-01-14
學位類別:碩士
校院名稱:國立臺灣科技大學
系所名稱:化學工程系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2015
畢業學年度:103
語文別:英文
論文頁數:113
外文關鍵詞:green processhydrogen peroxideordered structurepalladium-nickel
相關次數:
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  • 收藏至我的研究室書目清單書目收藏:0
過氧化氫(雙氧水)為對環境友善之工業用氧化劑。近期,鈀(Pd)與鈀金(PdAu)觸媒由於具有高選擇性與活性,吸引廣泛的注意。然而,昂貴黃金的使用限制其在工業上的廣泛應用。因此,研究上替代之催化金屬取代雙金屬中的黃金。
本研究將開發 PdxNiy鈀鎳雙金屬奈米觸媒於雙氧水之綠色合成。本研究發展一新穎擔體承載之觸媒於雙氧水直接合成反應。由於其鎳的價格遠低於金,因此被選為雙金屬的催化系統。首先,實驗分別採用硼氫化納(NaBH4)與氫氣來還原含鈀離子與鎳離子之前趨物,但結果顯示前者無法順利還原鎳離子,後者則無法在碳載體上將兩者還原成合金結構。
鑑此,考量觸媒需要高表面積與在酸性環境下之穩定性,本研究將利用酸處理後之碳與中孔碳在為載體。研究發現PdxNiy的雙金屬合金原本具有面心立方(face-centered cubic)的結構,在經過還原熱處理後轉變為面心四方(face-centered tetragonal)的結構。此有序結構之產生經證實可提高觸媒結構於酸性溶液下之穩定性與其產生雙氧水之活性。
It is well-known that hydrogen peroxide is a highly versatile environmentally friendly industrial oxidant. Recently, palladium and bimetallic palladium gold catalysts have come to prominence, due to their high selectivity and activity. However, the high cost of gold both limits their wide application in industry and at the same time fuels research into alternative catalytic metals able to replace gold in bimetallic catalysts.
This study focuses on PdxNiy bimetallic nanocatalysts for green production of hydrogen peroxide. In this work a new supported catalyst for the direct synthesis of hydrogen peroxide was developed. Nickel has been adopted as the catalytic candidate due to its low cost compared to gold. Two main approaches were taken to synthesize PdxNiy nanocatalysts. NaBH4 and H2 were applied as a reductive agent to reduce Pd2+ and Ni2+ in precursors to form bimetallic PdxNiy on pretreated-carbon, respectively. However, the analysis results show that NaBH4 was not able to reduce Ni2+, and the H2 reduction method cannot achieve desired interaction between nanocatalysts and support. Thus, mesoporous carbon support and the organic agent reduction method were further developed for the synthesis of bimetallic nanocatalysts which were characterized by the crystallographic face-centered-cubic structure.
Next, it is demonstrated that the alloy crystal structure of PdxNiy alloy can be arranged into the face-centered tetragonal (fct) structure after hydrogen treatment. Attributed to the ordered structure, the fct- PdxNiy catalyst found in this study enhances not only structural stability but also productivity with respect to the direct synthesis of hydrogen peroxide.
CHAPTER 1. INTRODUCTION 1
1.1. General Aspects and Uses of Hydrogen Peroxide 1
1.1.1. General aspects 1
1.1.2. Widespread application of hydrogen peroxide 2
1.2. The Production of Hydrogen Peroxide 4
1.3. About direct synthesis of Hydrogen Peroxide 7
1.4. Motivation 9
CHAPTER 2. LITERATURE REVIEW 11
2.1. Catalyst used in direct synthesis of Hydrogen Peroxide from Hydrogen and Oxygen 11
2.1.1. Direct synthesis of Hydrogen Peroxide in Pd-M bimetallic. 12
2.1.2. Direct synthesis of Hydrogen Peroxide in Pd-M bimetallic supported on pre-treated Carbon 15
2.1.3. Direct synthesis of Hydrogen Peroxide in Pd-M bimetallic catalysts by controlling crystal structure 19
2.2. Synthesis of Alloy PdNi/C Nanoparticles 21
2.3. Synthesis of Alloy Pd-M/C Nanoparticles with face center tetragonal 22
2.4. X-ray Absorption Spectroscopy 23
2.5. Electrochemical measurement for Hydrogen Peroxide Detection with rotating ring dish electrode 26
2.5.1. Collection efficiency of rotating ring disk electrode 29
2.5.2. Electrochemical measurement 29
CHAPTER 3. EXPERIMENTAL PROCEDURE 35
3.1. Materials and Equipment. 35
3.2. Methods for synthesis of Pd-Ni bimetallic catalysts 38
3.2.1. Direct Synthesis of PdNi alloy by using NaBH4 as a reducing agent 38
3.2.2. Direct Synthesis of PdNi alloy by using Hydrogen reduction 40
3.2.3. Direct synthesis of PdNi alloy on SBA-15 mesoporous support 43
3.3. Physical characterization of Catalysts 46
3.3.1. Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP – AES) 46
3.3.2. X-Ray Diffraction (XRD) 49
3.3.3. Field Emission Scanning Electron Microscope (FESEM) 51
3.3.4. TEM 52
3.4. Electrochemical measurement to detection Hydrogen Peroxide 54
CHAPTER 4. RESULTS & DISCUSSION 58
4.1. Catalyst characterization 58
4.1.1. XRD 58
4.1.2. XAS 64
4.1.3. ICP – AES 70
4.2. Surface property 72
4.2.1. SEM 72
4.2.2. TEM 75
4.3. Electrochemical measurement 79
4.3.1. Calibration curve 79
4.3.2. Reaction system 82
CHAPTER 5. CONCLUSION 93
REFERENCES 95
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